Lubricant containing condensation product



Patented Aug. 27, 1946 UNITED STATES PATENT OFFICE I LUBRICANT CONTAINING CONDENSATION PRODUCT Eugene Lieber, West New Brighton, Staten Island, N. Y., assignor to Standard Oil Development Company, a corporation of Delaware No Drawing. Application October 28, 1941,

Serial No. 416,825

This invention relates to a novel type of chem- ,ical' condensation products and to methods of pressors, to use some materials containing long-' chain aliphatic groups. Attempts have also been made in the past to produce pour depressors from aliphatic materials containing oxygen, such as esters, but successful pour-depressor results could only be obtained by using esters containing long-chain aliphatic groups, such as at least 10 or 12 carbon atoms and preferably more, such as 16, 18, 22, and the like.

It has now been found possible to make pour depressors from esters containing less than 10 carbon atoms by selecting special conditions for reacting them with a suitablearomatic compound, such as naphthalene. V

Broadly, the invention comprises the chemical condensation of lower esters, i. e., those having less than 10 carbon atoms with aromatic compounds in the presence of a Friedel -Crafts catalyst, using a sufliciently large amount of catalyst to efiect the desired condensation.

The esters to be used according to the present invention contain less than 10 carbon atoms and preferably less than 8 carbon atoms. The hydrocarbon groups in such esters should contain less than '7 carbon atoms. The acid radicals of.

these esters may originate from either'organic or inorganic acids, but the remaining portion of the ester should originate from organic hydroxy compounds, such as alkyl alcohols or phenols or substituted derivatives of such hydroxy comcompounds. When the esters are entirely organic they should contain at least one -CO0-R" group in which R is an aliphatic-hydrocarbon, preferably an alkyl radical, and they may have various general formulas such as the following:

7 Claims. (01. 252-57) Where R and R are saturated hydrocarbon radicals or unsaturated or chlorinated derivatives thereof, at least one, preferably R, being aliphatic and the other being aliphatic or cyclic in structure, and n being an integer of 1, 2, 3, or more. Specific examples of esters coming within .the general formulas described above include:

Methyl acetate Propyl acetate Butyl acetate Amyl acetate Methyl. butyrate Isjopropyl butyrate Di-isopropyl phthalate Di-ethyl carbonate Ethyl silicate Ethyl phosphate Amyl borate Methyl ester of monochloracetic acid I Amyl ester of propenoic acid Di-allyl phthalate. I Ally] acetate 'Also, if desired, mixtures of various esters may be used, especially commercial mixtures of materials which are isomeric or very similar in structure, as, for example, the product known as Pent-acetate, which is the acetic acid ester of a commercial mixture of amyl alcohols made from mixed amylenes, It is indeed very surprising that such condensation can be effected Withouthaving in the ester any reactive group, such as an o-lefinic linkage or a replaceable halogen atom, as is necessary in order to combine a paraflin wax molecule with naphthalene.

The aromatic compounds to be "used as the other primary raw material according to this invention may be of various types with the primary requisite that they contain one or more replaceable hydrogen atoms on the aromatic nucleus. 9f the-various types of aromatic compounds available,'the hydrocarbons are preferred, such as naphthalene, benzene, diphenyl, phenanthrene, toluene, amyl'benzene, retene (which is l-methyl '7-isopropyl phenanthrene), fiuorene (diphenylene methane); chrysene \(CIBHIZ), etc. lflrornatic compounds which may be considered Phenol Cresol Alpha-naphthol Anisol Beta-naphthol Amyl phenol Suitable nitrogen derivatives include aniline, toluidine, naphthyl amine, etc.

Of the condensing agents to be used Friedel- Crafts catalysts are preferred, and of these anhydrous aluminum chloride is preferred, but others may be used, such as ferric chloride, boron fluoride, antimony chloride, stannic chloride, and zinc chloride. Other condensation catalysts or condensing agents include sulfuric acid, hydrogen fluoride, activated clays, silica gels, semi-d1 vided metals, such as zinc, aluminum, etc. 7

Although the use of a solvent is optional this chemical reaction, it is to be preferred, and of the various materials suitable, hydrocarbon solvents, such as a refined kerosene, high-boiling naphtha, etc., may be mentioned, and various halogenated hydrocarbon solvents, such as tetrachlorethane, ethylene dichloride, chlorobenzene, dichloro benzene, etc. V

The proportions of the reactants to be used in carrying out this invention may be varied over a fairly wide range, as for instance, 0.2-5.0 mols, preferably 0.5-2.0 mols, of an ester for one mol of aromatic compound, the amount of catalyst of the Friedel-Crafts type, such as aluminum chloride, should be about 0.5.0 mols, preferably 1-3 mols, per mol of ester. amount thereof should be about 2-5 volumes per volume of mixed reactants. used for carrying out the reaction should notibe permitted to exceed 300 F., and preferably should be betweenthe approximate limits of room temperature and about 250 F. A convenient method of carrying out the reaction is to start the reaction at room temperature'until all of the materials have been added, and as the reaction begins to subside, to start the application of heat until a suitable elevated temperature, such as 150 F.

The temperature 4 shade. The product is soluble in mineral oils and is very useful therein for reducing pour point and at least in some cases it is also very useful as a green dye suitable as a lubricating oil dye, i. e.,

having a red through color and a green fiuorescence.

The pour-depressing value of this novel condensation product is due to its property of modifying the crystal structure of paraffin wax present in lubricating oils, for instance, when about Bil-10.0%, preferably 0.2-5.0%," of this wax modifier is added to a waxy lubricating oil such as a Pennsylvania type or other paraifinic lubricating oil having a relatively high pour point, the re-. sultant blend will have a substantially lower pour point; A small amount of this wax modifier is also useful as a dewaxing aid for removing wax from mineral lubricating oils of undesirably high wax content. In similarly small amounts, this wax modifier may also be incorporated into parafiin wax or compositions containing the same to be used for various purposes, such as coating or If a solvent is used, the

or 250 F. or more isreached and then to maintain such reaction temperature until the reaction has been completed, which will usually not take longer than 5 hours or so. After the reaction has been completed, the reaction mixture is preferably cooled and diluted with some solvent such as kerosene, or a halogenated solvent, preferably the same kind as was usedduring the reaction, if any was used then. After such cooling and dilution, the catalyst is hydrolyzed by contacting the reaction mass with water, dilute caustic soda, alcohol, and mixtures of such suitable media, and the resulting catalyst sludge is settled out and removed. The condensation products are then distilled either with fire and steam or with vacuum distillation, e. g., under an absolute pressure of 100 mm., mm., 20 mm., or even less of mercury, to a suitable temperature such as about 600 F. in order to remove solvent and.

low boiling products and to obtain asdistillation residue the desired high molecular'weight condensation product having pour depressing' and other valuable properties.

- This novel condensation product has a physical consistencyortemperature range'from a viscous oil to a resinous solid which may in some cases be very hard and brittle. Its color is usually green, brown, or black, or some intermediate impregnating papers or for making various molded products.

For the sake of illustration but without intending to limit the invention to the particular materials used, some experimental data are given.

herewith.

The procedure used in the first test will be discussed in detail and then the materials, propertions, and reaction conditions used in all of the tests, as well as the results obtained thereby, are

outlined in a table, it being understood that. the

process used for allof the tests is the same as that used in the first one,except when otherwise noted in they table. Incarrying out the first test, 118 grams of di-ethyl carbonate havingthe formula (Cal-I50) 200 and 128 grams of naphthalene were dissolved in 300 cc.-of kerosene (which had been highly pretreated with aluminum chloridebefore use in order to make it inert), contained in a suit-' able-reaction vessel fitted with a mechanical stirrer, thermometer, reflux condenser and means for heating and cooling. The stirrer was started and while maintaining the reaction mixture at -100 F. .266 grams of aluminum chloride were slowly added to the reaction mix ture over a period of one hour. "After'the addition of the aluminum chloride, the reaction-mixture was heated to 200- F; and maintained thereat for three hours. At the conclusion of this time, the reaction mixture was cooled and' diluted with a further quantity of'kerosene. The

aluminum chloride wasdecomposed by'the addi"v tion of water and the resulting kerosene extract Was washed free of acid. It wasthen distilled with fire and steam'to 600 F. in order to fremove solvent and low-boiling products. 132 grams of a bottoms residue comprising a brown resinous substance was obtained as product. When 2% of this condensation product was added to a waxy lubricating oil base stock having a pour point of +30 F., the, pour point was-lowered to '-15 F., thereby showing that this condensationproduct is an effective pour depressor.

It should be noted that in this first test, the

aluminum chloride was added last to the reaction vessel, whereas, as indicated in the table,

in many of the other'tests the aluminum chloride was mixed with the naphthalene or other aromatic compound, and the solvent,- and finally the ester was addedlast. In all the tests the reac tion was started at 90 F. and the final heating temperature was 200 F.

aromatic compound and a saturated ester hav ing less than 10 carbon atoms, said condensa- Table Ester Aromatic Kind Gms. Kind Gms.

Solvent (300 cc. 1

used) H1116, 1 point in Product 1"..- Diethylcarbonate 118 C1oHs 128 266 Kercglsene 6 o 2"... Amy] acetates (mixed) 1 98 Sec. but. acetate 116 0 011 128 266 Meti. aceto acetate 75 131 Tetralin-. 132 266 89 OtH 78 266 Tetrichlorethanefl o 131 0 0118-." 128 26g Keroisene 5 o 131 C Hg- 128 1 266 Tetrachlorethane 131 cam"--- 26 266 iiioseh'IIIII 100 0 135... 78 266 Tetrachlorethana.

132 15 Brown resinous.

139 ,5 DO. 3 154 5 Green oil.

128 Black oil green dye. 60 Brown viscous oil. 7 170 0 Green viscous oil.

Brown resinous green dye. 106 5 Red-brown resinous.

76 10 Brdittle black resinous green ye. 52 Brown resinous. 65 0 5%/-10 F. resinous. 26 25 Brown viscous oil. 32 5%/10 F. black resinous green dye.

town! comwwwoowcowm 1 Added last. 1 Made inert by heavy pretreatment with AlCla. I Distillation stopped at 500 F.

The above table of data shows that good pour depressors can be made from many diiTerent types of lower esters, such as diethyl carbonate, ethyl acetate, amyl acetate, secondary butyl acetate, and methyl aceto acetate, and they also show that these unexpectedly satisfactory results can be obtained by using a number of other difierent aromatic compounds and using'a substantially wide range of proportions of ester to aromatic compound. Good results were obtained both with a highly refined and inert kerosene as well as with tetrachlorethane as solvent. A number of the products not only were good pour depressors but also had the additional valuable property of being effective dyes suitable for imparting to the oil a green fluorescence or enhancing such property if it is already present to some degree. The most important pour depressor obtained was that produced in test 11 by reacting '75 grams of methyl aceto acetate with tion product being soluble in mineral oils, and substantially non-volatile at temperatures up to 600 F. under fire and steam distillation.

2. A lubricant according'to claim 1 containing a condensation product of an aromatic hydrocarbon and a saturated ester having less than 10 carbon atoms containing at least one COOR group in which R represents an alkyl radical.

3. Lubricant according to claim 1 containing the condensation product of an aromatic hydrocarbon and an ester of an alkyl alcohol and an acid selected from the group consisting of organic carboxylic acids and inorganic polybasic acids.

4. A lubricant comprising a major proportion of a waxy mineral lubricating oil and a small but pour-depressing amount of an anluminum chloride condensation product of about 1 mol of aromatic hydrocarbon and about 0.5 to 2 mols of saturated ester having less than 10 carbon atoms 128 grams of naphthalene using 266 grams of aluminum chloride (added last) in the presence of 300 cc. of tetrachlorethane, the materials being first mixed slowly at about 90 F. and then heated to about 200 F. for 3 hours, resulting in 52 grams of brown, resinous product, 2% of which reduced the pour point of a waxy mineral lubricating oil stock from +30 F. to -30 F.

The novel condensation products of this invention may, if desired, be added to other types of lubricating oil base stocks, such as those derived 55 from naphtheni'c or mixed naphthenic-paralilnic base crudes, and may also be added to other types of petroleum fractions, such as naphtha, gasoline, kerosene, fuel oil, Diesel oil, etc.

It is not intended that this invention be limited to any of the specific examples, which have been given merely for the sake of illustration, but only by the appended claims in which it is intended to claim all novelty inherent in the invention as well as any equivalents coming with- 5 in the scope and spirit of the invention.

I claim:

1. A lubricant comprising a major proportion of lubricating oil and a pour-depressing amount of a Friedel-Crafts condensation product of an of an alkyl alcohol having less than 7 carbon atoms and a fatty acid having less than '7 carbon atoms, said condensation product being soluble in mineral oils and being substantially nonvolatile at temperatures up to 600 F. under fire and steam distillation.

5. A lubricant comprising a major proportion of waxy mineral lubricating oil and a small but pour-depressing amount of a Friedel-Crafts condensation product of an aromatic compound and a saturated acetoacetate ester having less than 10 carbon atoms, said condensation product be-- ing soluble in mineral oils and being substantially non-volatile at temperatures up to 600 F. under fire and steam distillation.

6. Lubricant according to claim 5 containing a condensation product of naphthalene and methyl acetoacetate. l

7. A lubricant comprising a major proportion of a waxy mineral lubricating oil and a small but pour-depressing amount of a Friedel-Crafts condensation product of an aromatic hydrocarbon and ethyl acetate, said condensation product being soluble in mineral oils and substantially non volatile at temperatures up to 600 F.; under fire and steam distillation. 4

' EUGENE LIEBER. 

